Anderson, JC;
Chang, CH;
Corpinot, MK;
Nunn, M;
Ware, OJ;
(2019)
Investigation of the [1,5]-hydride shift as a route to nitro-Mannich cyclisations.
Tetrahedron
, 75
(48)
, Article 130663. 10.1016/j.tet.2019.130663.
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Abstract
Conditions were found for the [1,5]-hydride shift nitro-Mannich reaction that led to the synthesis of 2,3-disubstituted tetrahydroquinolines. Two simple cyclic amine substrates gave diastereomerically pure rearranged products in 65 and 90% yields by refluxing in HFIP. A more general procedure used Gd(OTf)3 as a catalyst and successfully rearranged other cyclic and acyclic amines in 42–84% yield with diastereomeric ratios of 75:25 to >95:5 in favour of the anti-diastereoisomer (9 examples). Two examples of sulphur containing heterocycles gave lower yields of 9 and 25%. Electron withdrawing substituents were shown to have a deleterious effect on the success of the reaction. The results indicated the limitation of the [1,5]-hydride shift nitro-Mannich reaction with respect to the stability of the intermediate iminium ion.
| Type: | Article |
|---|---|
| Title: | Investigation of the [1,5]-hydride shift as a route to nitro-Mannich cyclisations |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1016/j.tet.2019.130663 |
| Publisher version: | https://doi.org/10.1016/j.tet.2019.130663 |
| Language: | English |
| Additional information: | This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. |
| Keywords: | [1,5]-hydride shift, Nitro-Mannich, Tetrahydroquinolines, HFIP promoted, Gd(OTf)3 catalysis |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10084860 |
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